WO1998030622A1 - Procede de production de caoutchouc modifie en surface, caoutchouc modifie en surface et materiau d'etancheite - Google Patents

Procede de production de caoutchouc modifie en surface, caoutchouc modifie en surface et materiau d'etancheite Download PDF

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Publication number
WO1998030622A1
WO1998030622A1 PCT/JP1997/004831 JP9704831W WO9830622A1 WO 1998030622 A1 WO1998030622 A1 WO 1998030622A1 JP 9704831 W JP9704831 W JP 9704831W WO 9830622 A1 WO9830622 A1 WO 9830622A1
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Prior art keywords
rubber
monomer
modified rubber
modified
producing
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PCT/JP1997/004831
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English (en)
Japanese (ja)
Inventor
Shinya Sakurai
Yukio Kobayashi
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Nippon Valqua Industries, Ltd.
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Priority to EP97950398A priority Critical patent/EP0890601B1/fr
Priority to US09/142,531 priority patent/US6074698A/en
Priority to KR1019980707108A priority patent/KR100525065B1/ko
Priority to DE69735938T priority patent/DE69735938T2/de
Publication of WO1998030622A1 publication Critical patent/WO1998030622A1/fr
Priority to HK99104303A priority patent/HK1019153A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2315/00—Characterised by the use of rubber derivatives
    • C08J2315/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • the present invention relates to a method for producing a surface-modified rubber, a surface-modified rubber, and a seal material.
  • Surface modification to obtain rubber with excellent low friction, non-adhesion, abrasion resistance and plasma resistance while maintaining compression set, rubber elasticity, mechanical strength and deformation followability
  • the present invention relates to a method for producing rubber, a surface-modified rubber, and a sealing material obtained from the surface-modified rubber.
  • Rubber molded articles are widely used as sealing materials for, for example, chemical equipment, semiconductor manufacturing equipment, chemical liquid piping / tanks, food manufacturing equipment, and the like.
  • Techniques for imparting low friction, non-adhesiveness, and abrasion resistance to such a rubber molded article include the following methods of modifying the rubber material itself as described in 1 to 2, and 3 to 5. There are known methods for modifying the surface of a rubber material or its vicinity as shown below.
  • cross-linking agent impregnation method A method of impregnating a cross-linking agent on the surface of a rubber molded body and promoting cross-linking near the rubber surface by heating (cross-linking agent impregnation method)
  • the solid lubricant addition method (2) has low friction and non-adhesive properties because the solid lubricant mixed in the rubber material does not protrude easily onto the surface of the rubber molded product. Functions are not sufficiently exhibited.
  • the above function can be improved by adding a large amount of a solid lubricant to the rubber base material in order to improve the above function of the rubber material surface.
  • the mechanical strength and rubber elasticity of the obtained rubber molded article tend to decrease, and the followability to the mating material tends to be poor, and the compression set tends to increase.
  • the mechanical strength of the obtained rubber molded product is small, and the bleeding speed of the oil mixed in the rubber material is large, and the bleeding amount depends on the bleed amount.
  • Phenomena such as the lubricity of the rubber molded body surface differing and the friction coefficient of the rubber molded body sharply increasing after the completion of bleeding, and the rubber molded body was stable for a long period of time. Lubricity cannot be maintained. There is also a problem that oil oozing out of the rubber molded article may contaminate the mating material.
  • the rubber that constitutes the obtained resin-coated molded product Since the adhesion between the molded body and the surface coating layer may be reduced, it is not suitable for use in a dynamic state by actually incorporating it into a device as a sealing member. Rubber elasticity tends to decrease, resulting in poor follow-up to the mating material.
  • the rubber material surface is cross-linked to increase the surface hardness and to reduce its contact area with the mating surface, thereby achieving its function.
  • the composition itself of the surface of the rubber molded article is not different from that of other parts, and therefore the level of function expression depends on the degree of surface cross-linking.
  • a monomer compatible with the rubber material is used as a monomer to be impregnated and polymerized in a rubber material. Only monomers having a relatively small molecular weight, such as (meth) acrylic acid and derivatives thereof, such as (meth) acrylic acid and derivatives thereof, are capable of being diffused into a rubber network chain. Poorly diffused near the material surface, poor if rubber material and monomer are poorly compatible The higher the molecular weight of the monomer, the more difficult it is to impregnate and diffuse the monomer near the surface of the rubber material. It is also difficult to effectively exhibit functions such as adhesiveness and abrasion resistance on the surface of the rubber molded product.
  • a silicone-based monomer and a fluorine-based monomer are impregnated and diffused in the vicinity of the surface of a wide range of rubber materials and polymerized to produce low friction and non-adhesive properties.
  • this surface polymerization curing method ⁇ ⁇ if the surface hardness of the obtained rubber molded body increases, fine cracks are likely to be generated on the surface similarly to the above-mentioned cross-linking agent impregnation method ⁇ , and the mating surface may be damaged. Deformation follow-up properties tend to decrease, and sealing properties may decrease.
  • the surface of the rubber material or its vicinity is used.
  • the rubber material itself can be improved in terms of mechanical strength, compression set, rubber elasticity, etc. There is a problem that physical properties deteriorate,
  • the vicinity of the surface of the obtained rubber molded body is hardened to form a fine crack.
  • the cross-linking agent impregnation method 4 and the surface polymerization curing method 5 the vicinity of the surface of the obtained rubber molded body is hardened to form a fine crack.
  • cracks occur and the ability to follow the deformation to the mating surface is reduced.
  • adhesion between the rubber material and the surface coating layer becomes poor due to lack of compatibility with the rubber material.
  • Japanese Patent No. 2536677 Japanese Unexamined Patent Application Publication No. 1301725 discloses a process for vulcanizing fluororubber to form a double bond in the fluororubber.
  • a production method is disclosed, and the step of infiltrating the reactive silicone resin into the surface of the fluorine rubber includes the step of dissolving the reactive silicone resin in a solvent such as acetate.
  • a method of immersing fluorine rubber in a silicone resin solution is mentioned.
  • the rubber capable of non-adhesive treatment on the surface is limited to a fluorine rubber having a double bond introduced therein, and the type of the surface modifier usable for the surface treatment is also limited. Limited.
  • a reactive silicone resin is used as a surface modifier. Since this silicone resin is a polymer compound, even if the rubber base material is swollen with a solvent as described in the patent document, Since the molecular weight is too large, it is difficult to impregnate the rubber from the inside to the inside.
  • the rubber moldings made of various materials are excellent in heat resistance, chemical resistance and plasma resistance, and the polymer itself is stable. It does not contain impurities such as anti-aging agents commonly used in other rubber bases that can cause contamination of semiconductor products, etc., so the material itself has excellent purity.
  • the advantage Yes it is used as a sealing material for liquid crystal / semiconductor manufacturing equipment, food industry, etc.
  • this fluororubber molded article when it is attached to the opening / closing part of an apparatus, it has a property of being easily adhered to a mating material (also referred to as “adhesiveness. Adhesiveness”). There is a problem that the opening and closing workability is poor. Moreover, this sticking property tends to become more pronounced as the fluororubber sealant is used at higher temperatures, and in conventional fluororubber moldings, it is often used at temperatures higher than room temperature. As a sealing material for the above-mentioned liquid crystal and semiconductor manufacturing equipment, for the food industry, etc., there was room for improvement in terms of low friction and non-adhesion.
  • a plasma generator has been used as a semiconductor device.
  • plasma processing is typified by a plasma generator.
  • the sealing material of the device is required to have durability against plasma and not release gas etc. from the sealing material itself so that a clean vacuum state in the chamber or the like can be maintained. Such properties (low outgassing) are also required.
  • the present invention is intended to solve the problems associated with the prior art as described above, and is intended to solve the problems inherent in rubber materials such as strength, compression set, sealability, deformation followability, etc.
  • a rubber molded product that can exhibit functions due to the structure of the monomer used, such as excellent non-adhesion, low friction, abrasion resistance and plasma resistance, and ozone resistance and oil resistance, is obtained.
  • the present invention is excellent in non-adhesiveness, low friction, abrasion resistance, and plasma resistance while maintaining properties inherent in rubber materials such as strength, compression set, sealability, deformation and followability. It is an object of the present invention to provide a surface-modified rubber capable of exhibiting functions derived from the structure of the monomer used, such as ozone resistance and oil resistance, and a sealing material using such a surface-modified rubber. are doing.
  • the monomer is polymerized, thereby modifying the surface of the rubber substrate and its vicinity.
  • the treatment liquid is brought into contact with a rubber substrate, and the rubber substrate is impregnated with a polymerizable double bond-containing monomer and a polymerization initiator. It is preferable to polymerize the monomer.
  • the contact-treated rubber base material is used in the presence of oxygen molecules of 1.0 xl 0 t 9 Zcm 3 or less, preferably 5.6 ⁇ 10 18 / cm 3 It is desirable to heat under the following conditions.
  • the polymerizable double bond-containing monomer is It is preferable to use a styrene-containing unsaturated fluorine-containing compound and a Z- or styrene-unsaturated organosiloxane, and in particular, the monomer having a polymerizable double bond is an ethylene-unsaturated monomer. Preferably, they are organosiloxanes.
  • the rubber substrate is a fluorine rubber.
  • the rubber base material is immersed in the above-mentioned processing liquid, thereby bringing the processing liquid into contact with the rubber base material.
  • the surface-modified rubber according to the present invention is characterized by being obtained by the above-described production method. Further, the surface-modified rubber is preferably used for a sealing material, and the sealing material is preferably used for a liquid crystal / semiconductor manufacturing apparatus, more preferably, for the sealing material. It is desirable that the material is a seal material for a plasma processing apparatus.
  • low friction, non-adhesion, abrasion resistance, and plasma resistance are maintained while maintaining the inherent rubber elasticity, compression set, mechanical strength, and deformation followability of the rubber material. It is possible to obtain a surface-modified rubber having excellent properties and exhibiting functions derived from the structure of the monomer used, such as ozone resistance and oil swelling resistance (oil resistance), and a sealing material using the rubber.
  • Fig. 1 shows the friction and wear test equipment used in the examples and comparative examples of the present invention. (It is a principle explanatory diagram of a Matsubara type friction and wear tester.
  • FIG. 2 is a diagram illustrating the principle of a Haydon surface property tester for measuring a friction coefficient in an example of the present invention.
  • FIG. 3 is a view showing a sticking force measuring device used in the present invention.
  • a treatment liquid (a) containing a polymerizable double bond-containing monomer, a polymerization initiator (preferably a radical polymerization initiator) and a solvent is brought into contact with a rubber base (b). Thereafter, by heating the obtained contact-treated rubber substrate, the monomer is polymerized to modify the surface of the rubber substrate and the inside of the rubber substrate (particularly, the vicinity of the surface).
  • the treatment liquid (a) containing a polymerizable double bond-containing monomer, a radical polymerization initiator, and a solvent will be described.
  • the polymerizable double bond-containing monomer contained in the treatment liquid (a) is a monomer having one or more polymerization-reactive double bonds in a molecular skeleton.
  • the monomer having an unsaturated double bond include (i) ethylenically unsaturated fluorine-containing compounds and (ii) ethylenically unsaturated organosiloxane, and in the present invention, (i) Alternatively, either (ii) may be used alone, or both (i) and (ii) may be used in combination.
  • ethylenically unsaturated fluorine-containing compounds and ethylenically unsaturated organosiloxanes have low friction and non-adhesive properties.
  • the macromonomer generally refers to a compound having a molecular weight of about several hundreds to several tens of thousands, having a polymerizable functional group, and being regarded as a monomer.
  • a treatment liquid comprising the monomer, a polymerization initiator, and a solvent compatible with both of them is used in the present invention. Since the rubber base material (b) is treated using (a), the rubber base material can be impregnated with these components satisfactorily. A molded rubber article can be obtained.
  • the rubber molded body is plasma-resistant for sealing materials for liquid crystal / semiconductor manufacturing equipment, for plasma processing equipment, etc., especially when the gas type is oxygen or a gas containing oxygen.
  • the monomer having a polymerizable double bond is an ethylenically unsaturated fluorine-containing compound (i) or an ethylenically unsaturated monomer.
  • they are lenic unsaturated organosiloxanes (ii).
  • the ethylenically unsaturated fluorine-containing compounds (i) are useful for imparting low friction and non-adhesion to a rubber molded article.
  • fluorine-based polymers themselves have properties (plasma resistance) that are less susceptible to plasma compared to hydrocarbon-based rubber.
  • a general synthetic rubber other than fluororubber eg, NBR, SBR, EPDM, etc.
  • the ethylenically unsaturated organosiloxanes (ii) include dimethylsiloxane, methylphenolinolesiloxane, trimethylphenolenole siloxane, etc., which impart low friction, non-adhesiveness, and plasma resistance to the rubber base material.
  • a polymerizable monomer such as alkylene oxide, silyl perylene, silethylene, styrene, or the like is copolymerized at a site derived from the homopolymer or copolymer of the organosiloxane, or The site derived from the homopolymer or copolymer of the above organosiloxane may be modified by bonding a polymer such as polystyrene, nylon, or polyurethane. .
  • the functional group having an ethylenic bond may be present at one or both ends of the ethylenically unsaturated fluorine-containing compound (i) and the ethylenically unsaturated organosiloxane (ii). Also, it may be present in the side chain (branch).
  • the number of ethylene bonds present in the ethylenically unsaturated fluorine-containing compound (i) and the ethylenically unsaturated organosiloxane (ii) is not particularly limited as long as it is one or more. .
  • Examples of the ethylenically unsaturated fluorine-containing compounds (i) include:
  • the fluorine-containing alcohol may have a branched chain composed of a lower alkyl group having about 1 to 5 carbon atoms, a 10 H group, or the like.
  • - main chain carbon atoms in the Le is "- S 0 2 N (R) one", etc. rather it may also be substituted by, R in the "one S 0 2 N (R) one" is hydrogen It represents an atom or an alkyl group having about 1 to 10 carbon atoms. ]
  • the molecular weight of such ethylenically unsaturated fluorine-containing compounds (i) is usually from 100 to 100,000 (10,000), preferably from 150 to 500,000. More preferably, it is about 200 to 100,000.
  • Examples of such ethylenically unsaturated fluorine-containing compounds (i) include the compounds of compound numbers (i-1) to (i-54) shown in Tables 1 to 5 below. Among these, the compounds of the compound numbers (i-1) to (i-8) are included in 2, and the others are included in 1.
  • Ci-3) (Perfluorooctyl) ethylene
  • Ci-8) 1,8-divinylhexadecafluorooctane
  • Ci-2fl 3- (Perfluoro mouth-7-methyloctyl) -2-hydroxypropizole methacrylate
  • Ci-33) 1,2,3,4,4,4-hexafluorobutyl acrylate
  • Ci_-35 3-Perfluorobutyl-2-hydroxypropyl acrylate
  • Ci- 2- (Perfluoro mouth-7-methyloctyl) ethyl acrylate
  • the compounds (ii-1) to (ii7) have an ethylenic property having a vinyl group or an isopropenyl group at both ends.
  • Unsaturated organosiloxanes (ii)
  • the compounds (ii-8) to (ii-13) are ethylenically unsaturated organosiloxanes (ii) having a vinyl group or an isopropenyl group at one end,
  • the compounds (ii-14) to (ii-17) are ethylenically unsaturated organosiloxanes (ii) having a vinyl group or an isopropenyl group in the side chain.
  • the molecular weight of such ethylenically unsaturated organosiloxanes (ii) is usually from 100,000 to 100,000, preferably from 200,000 to 50,000, and more preferably from 200,000 to 50,000. It is between 250 and 25,000.
  • the viscosity (measured at 25 ° C.) of the ethylenically unsaturated organosiloxane (ii) is usually from 10,000 to 20,000 cst; and preferably from 2 to 15,000 cst. Preferably it is 3 to 5000 est. These organosiloxanes can be used alone or in combination of two or more. [Table 6]
  • I CH 2 CH-Si-0- Si-0 ⁇
  • the polymerization initiator various conventionally known ones such as a radical polymerization initiator, a cation polymerization initiator, and an anion polymerization initiator may be used.
  • the radical polymerization initiator is used. Is preferably used.
  • the radical polymerization initiator include inorganic or organic peroxides, azo compounds, organometallic compounds, and metals.
  • the inorganic or organic peroxide include 35, 6-trichloroperfluorohexanolyl peroxide, ammonium persulfate, hydrogen peroxide, and the like.
  • the metal include azobisisobutyrate, and examples of the metal include LiKNaMgZnHgA1. Of these, organic peroxides are preferably used.
  • organic peroxides include digipolaxide, 24-dichlorobenzene benzoinoleno, o-oxide, g-butyl chloroperoxide, and t-butynolemic.
  • a polymerizable double bond-containing monomer and a polymerization initiator can be dissolved, and if it is possible to swell the rubber substrate, poor compatibility with the rubber substrate 1 Even if it is a kind of polymerizable double bond-containing monomer or a mixture of two or more kinds of polymerizable double bond-containing monomers, it can be easily impregnated (penetrated) into the rubber substrate and diffused. Because it is possible, it is not particularly limited and can be widely used.
  • the above-mentioned function is used as the solvent regardless of the amount of the polymerizable double bond-containing monomer that can be dissolved (large or small solubility) or the degree of swelling of the rubber base material.
  • a solvent that has high solubility for the polymerizable double bond-containing monomer and high swelling of the rubber substrate is preferable.
  • a polymerizable double bond-containing monomer is usually added in an amount of 0.05 part by weight at 20 ° C. to 100 parts by weight of the solvent.
  • those which can be dissolved in an amount of preferably at least 0.05 part by weight, more preferably at least 0.1 part by weight are preferable.
  • Specific examples of the solvent usable in the present invention include ketones such as acetate and MEK (methylethyl ketone);
  • Aliphatic and aromatic hydrocarbons such as hexane, heptane, toluene, xylene, THF (tetrahydrofuran), benzene, rigoin, and isoparaffin;
  • CC 1 F 3 Click throat Application Benefits Furuorome data down (CC 1 F 3), CC 1 F - off b emissions such as CF (halogenated hydrocarbons);
  • Ethers such as dioxane, ethyl ether and isopropyl ether;
  • Esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; These solvents may be used alone or in combination of two or more, and are appropriately selected according to the rubber base material used.
  • the solvent may be distilled off at any time during or after the reaction of the monomer. However, when the solvent participates in any bonding on the surface or inside of the rubber substrate, it may not be distilled off.
  • the treatment liquid (a) may further contain methyl hydridic silicone oil or the like. Depending on the material, the low friction and non-stickiness of the obtained rubber molded article can be improved.
  • the rubber base material is a fluoro rubber (FKM-based rubber) as described later
  • the treatment liquid (a) contains methylhydrodisiloxane silicone oil
  • the mating material becomes In particular, aluminum and SUS are preferred because the surface modified rubber has better non-adhesiveness.
  • the polymerizable double bond-containing monomer in the treatment liquid (a), is usually contained in an amount of 0.1 to 100 parts by weight, preferably 100 to 100 parts by weight of the solvent.
  • the polymerization initiator especially the radical polymerization initiator, is usually used in an amount of 0.01 to: L0000 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the solvent. It is desirable to use it in a concentration range of from 0.5 to 100 parts by weight, more preferably from 0.5 to 100 parts by weight.
  • the concentration of the polymerizable double bond-containing monomer is less than 0.1 part by weight with respect to 100 parts by weight of the solvent, the presence of the monomer on the surface of the rubber base material to be treated is reduced. If the amount is too small, and if it exceeds 1000 parts by weight, the swelling effect of the solvent on the rubber base material is reduced, so that the monomer is effectively impregnated on the rubber surface and its vicinity (that is, inside the rubber base material). Tends to be difficult to spread.
  • the concentration of the polymerization initiator is less than 0.01 parts by weight with respect to 100 parts by weight of the solvent, the radical generation concentration is too low and the monomer is subjected to a polymerization reaction on and near the rubber substrate surface.
  • the resulting polymer cannot be effectively fixed in the rubber molecular chain on the rubber substrate surface or near (inside) the rubber substrate surface, and the weight is 100,000.
  • the amount exceeds the part the amount of the component based on the polymerization initiator at the rubber surface and in the vicinity thereof becomes so large that the chemical structure of the monomer, for example, the effect of reducing the adhesiveness of the portion caused by the siroquine bond becomes small.
  • the polymerization initiator which is originally used to cause the monomer to undergo a polymerization reaction and immobilize it on the rubber substrate (also called reaction and immobilization), crosslinks near the rubber surface as its concentration increases.
  • a rubber surface to increase the amount consumed in reaction They tend to result in an adverse effect on the click rack Yui Bitsuki sealing properties.
  • the effect of exhibiting low friction, non-adhesion and abrasion resistance tends to be significantly impaired.
  • the above treatment solution containing a polymerizable double bond-containing monomer, a polymerization initiator and a solvent is brought into contact with a rubber substrate to form a polymerizable double bond in the rubber substrate. Impregnated with contained monomer and polymerization initiator
  • the surface of the rubber substrate or the vicinity thereof (that is, the inside of the rubber substrate) is subjected to the reforming force, as described above.
  • the mechanism is not clear.
  • a polymerizable polymer containing a polymerizable double bond is initiated by a polymerization initiator to form a polymer.
  • the rubber molecular chains or bases constituting the base material are immobilized on the rubber base material by being partially entangled in the rubber molecular network, and in some cases, some polymerizable double bonds.
  • a reaction between the contained monomer or a part of the polymer and the rubber substrate occurs, and the monomer or the polymer is immobilized on the rubber substrate, and the surface of the rubber substrate or the vicinity thereof is modified. It is speculated that this will be done.
  • methylhydrogensilicone corn oil which is added as required, is used in an amount of 0 to 100 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the solvent. It is used in a concentration range of 0 parts by weight, more preferably from 0 to 50 parts by weight.
  • the rubber substrate (b) used in the present invention is not particularly limited in terms of material, shape, dimensions, etc., and various conventionally known rubber substrates can be used. Examples include NBR, HNBR, SBR, ACM, U, FKM, Q, CR, NR, IIR, BR, and the like. Of these rubber substrates, the rubber substrate is peroxide A crosslinkable rubber substrate allows the monomer to be more effectively polymerized and immobilized in the rubber substrate, and is non-adhesive, low-frictional, abrasion-resistant, and plasma-resistant. It is preferable because it can express functions such as.
  • the rubber base is a rubber base capable of cross-linking peroxyde
  • the monomer is polymerized, but also the monomer is formed on the rubber molecular chain in the rubber base by a graph and Z.
  • the surface of the rubber substrate or in the vicinity of the surface must be exposed to functions such as abrasion resistance, low friction, non-adhesion, and plasma resistance. It is presumed to be effective.
  • the peroxide crosslinkable rubber substrate is a fluororubber (FKM) because the non-adhesiveness, abrasion resistance, compression set and the like are further improved.
  • FKM fluororubber
  • Vinylidene fluoride encompassesohexafluoropropylene copolymer, vinylidene fluoride Z trifluorochloroethylene copolymer, vinylidene fluoride Z penfluorene propylene copolymer Binary vinylidene fluoride rubber such as copolymer;
  • 5Vinyl fluoride Fluoride Denfluorotetrafluoroethylene Z Hexafluoropropylene copolymer, Vinylidene fluoride Z tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, Vinyl fluoride Ternary rubber such as den Z tetrafluoroethylen Z propylene copolymer;
  • thermoplastic fluororubber may be subjected to a crosslinking treatment such as radiation crosslinking.
  • a crosslinking treatment such as radiation crosslinking.
  • tetrafluorofluoroethylene vinyl ether copolymer is used.
  • Crosslinking treatment such as radiation crosslinking may also be applied to (2).
  • radiation-crosslinked products include, for example, DuPont's “Carrelets” and Daikin Industries' “Perflo”. Is mentioned.
  • the thermoplastic fluororubber includes an elastomeric polymer chain segment and a non-elastomeric polymer chain segment, and is a combination of these segments. At least one of them is a fluorine-containing polymer single-chain segment, and at temperatures near room temperature, the elastomeric polymer chain segment has some form. It shows rubber elasticity because plastic deformation is prevented, but shows plastic deformation when the temperature rises and the hard block formed from non-elastomeric polymer chain segments softens. A thing.
  • thermoplastic fluororubber is a chain consisting of the above-mentioned elastomeric polymer chain segment (i) and the non-elastomeric polymer chain segment (ii).
  • the iodine atom at one end of this chain It consists of an iodide compound at the other end of the chain and a residue obtained by removing at least one iodine atom.
  • C It is a copolymer of monofluoroalkyl vinyl ether / tetrafluoroethylene Z-fuzivinylidene (molar ratio: 15 to 75, 0 to 85/0 to 85), and has a molecular weight of 30, 000 (30,000) to 1,200,000 (1,200,000).
  • non-elastomeric polymer single-chain segment (ii) is non-elastomeric polymer single-chain segment (ii)
  • thermoplastic fluororubbers the elastomeric polymer single-chain segment (1) described above and
  • the non-elastomeric polymer chain segment of (4) is preferably used.
  • thermoplastic fluororubber Details of such thermoplastic fluororubber are disclosed in Japanese Patent Application Laid-Open No. 53-334.
  • Japanese Patent Publication No. 95 and Japanese Patent Publication No. Hei 6-53 238 are examples of such elastomers.
  • Daikin Industries Co., Ltd. Products sold under the trade name “Balflon Cristal Lava Ichi” by Nippon Barka Ichi Kogyo Co., Ltd. (both are discharge-crosslinked products).
  • the fluororubber (FKM) only needs to include the above-mentioned polymers (1) to (4), and the fluororubber is derived from other monomer power. Units may be introduced, and the polymers of (1) to (5) may be modified. Further, the polymer may contain any one or more of the above-mentioned polymers.
  • Examples of the shape of the rubber substrate used in the present invention include, for example, a sheet shape, a plate shape, a bar shape, a ring shape, various complicated block shapes, and the like, depending on the intended use. It is not particularly limited.
  • a polymerization initiator preferably a radical polymerization initiator
  • the rubber substrate may be immersed in the treatment liquid, or the treatment liquid may be applied to the rubber substrate. May be applied by spraying or the like, may be applied by a brush or the like, and may employ various conventionally known contact methods. It is preferable to immerse in (a).
  • the amount of rubber substrate impregnated with the treatment liquid and the amount of swelling of the rubber substrate are determined by the type and molecular weight of the monomer in the treatment liquid used, the type of rubber, the rubber crosslink density, the type of polymerization initiator, It differs depending on the type of solvent, the concentration of the processing solution, the contact time (immersion time) between the above-mentioned processing solution and the rubber substrate, the immersion temperature, or the storage period from contact with the processing solution until heat treatment. Not decided.
  • the treatment liquid (a) containing the polymerizable double bond-containing monomer, the polymerization initiator, and the solvent in the amounts described above, respectively, and the rubber substrate (b), When contacting at a temperature of 15 to 25 ° C and normal pressure (1 atmosphere), it is usually 0.1 seconds or more, preferably 1 second to 1 month, and more preferably. The contact is preferably performed for about 1 second to about 72 hours, and more preferably, the rubber substrate (b) is immersed in the treatment liquid (a) under such conditions. Is desirable.
  • the following heat treatment may be performed immediately, or after about one month, the following heat treatment may be performed.
  • the treatment liquid penetrates deeply with time before reaching equilibrium, but when equilibrium swelling is reached. Impregnation / diffusion apparently stops.
  • the monomers in the treatment liquid (a) which diffuse and permeate into and out of the rubber base material surface are removed from the rubber base material with the passage of time.
  • the monomer that has been diffused and infiltrated (impregnated) must be at least completely bleed out.
  • the storage temperature of the rubber substrate after the contact treatment is lower than room temperature, for example, +10.
  • room temperature for example, +10.
  • the temperature By setting the temperature to C 21 ° C, it is possible to suppress the bleeding rate of the treatment liquid (a). Therefore, under such a low temperature, the solvent-treated rubber base material can be stored without being subjected to the heat treatment as described below, so that the time from the immersion treatment to the heat treatment is particularly short.
  • the solvent-treated rubber base material can be stored without being subjected to the heat treatment as described below, so that the time from the immersion treatment to the heat treatment is particularly short.
  • at normal temperature and pressure after the contact treatment, it can be stored for the above period, that is, about 1 second to 1 month until the heat treatment.
  • the rubber substrate (b) contact-treated rubber substrate treated with the treatment liquid (a) is heated to induce a polymerization initiator, preferably a radical polymerization initiator.
  • a polymerization initiator preferably a radical polymerization initiator.
  • this volume is the number of (spatial, either good in the liquid) oxygen molecules present in 1 m I (1 cm 3)
  • the condition (environment) is 1.0 X 10 19 or less, and more preferably, the number of oxygen molecules is 5.6 X 10 18 or less, Z m 1.
  • the number of oxygen molecules present per unit volume The smaller the number, the more preferable for effective reaction and immobilization of the monomer.
  • the volume percentage of oxygen, excluding water vapor, of the chemical components in the atmosphere occupies about 20.993%, and in the atmosphere at 0 ° C, 1 atm, and 1 m1, There are about 5.6 X 10 18 oxygen molecules.
  • the above-mentioned manner for example atmospheric pressure under a reduced pressure of not more than (the number of oxygen molecules 5. 6 X 1 0 1 8 pieces
  • the following conditions of Z m 1 and the following ( ⁇ )) can be adopted.
  • the gas used here is not particularly limited as long as it is a gas (gas) that does not inhibit the polymerization reaction such as the above-mentioned radical reaction.
  • the above-mentioned gases such as the above-mentioned carbon dioxide gas, nitrogen gas, helium gas, etc. (Gas) is preferably used.
  • Oxygen concentration at the reaction site is lower than that in the atmosphere, for example, by reacting in a liquid such as oil-solvent, or by applying these liquids to the surface of a rubber substrate and performing the above radical reaction under heating.
  • the number of oxygen molecules existing in 1 m 1 of space is 1.0 ⁇ 10 1 9 or less favored by rather is 5. 6 x 1 0 18 or less as long as an environment, not particularly limited.
  • the heat treatment under the above-mentioned conditions is performed by polymerizing the polymerizable double bond-containing monomer impregnated in the rubber base material and permeating and diffusing by a radical reaction, etc.
  • a radical reaction etc.
  • it is not particularly limited as long as it can be immobilized inside, it is usually at a temperature of 35 to 400 ° C, usually for 1 second to 720 hours, preferably at a temperature of 50 to 350 ° C. It is performed for 1 second to 72 hours at the temperature.
  • the polymer containing a polymerizable double bond impregnated in the rubber base material and permeating and diffusing is radically cured by the thermally decomposed radical polymerization initiator. It reacts and polymerizes and is immobilized in the rubber substrate and on the surface of the rubber substrate. Note that if the heat treatment temperature is raised in the above range, the monomer bleeding speed does not increase so much, and if the polymerization reaction speed increases remarkably, the higher temperature, for example, By heating the rubber substrate at a temperature of 100 to 300 ° C., the rubber substrate can be modified to a deeper depth.
  • the depth at which the polymerizable double bond-containing monomer in the processing solution ( a ) is fixed by reaction that is, the rubber group
  • the distance from the surface of the material in the inward direction is determined by the concentration of the treatment solution (a), the immersion time in the treatment solution (a), the reaction speed, and the pre-
  • the processing depth in other words, the The thickness of the layer that is reacted and fixed (reaction fixing layer) can be adjusted.
  • the rubber base material (b) is immersed in the treatment liquid (a) for a long time, and after immersion, heat treatment is performed as soon as possible.
  • a polymerization reaction such as a radical reaction is preferably performed.
  • the temperature of the heat treatment is increased, in a system where the rate of the radical reaction is remarkably increased rather than the rate of the monomer bleed due to the increase in the temperature, the temperature is increased to improve the depth of the rubber base material. Processing can proceed.
  • the depth (thickness) of the portion that is judged to be clearly reformed as a result of such a reforming process is, for example, when the rubber base material is HNBR-based rubber, 100 to 100 parts by weight of methacrylic acid-modified silicone oil (in the case of two or more types, the total amount) 5 to 20 parts by weight, and dimethyl peroxide 0.5 to 3 parts by weight After immersing the HNBR-based rubber base material with a thickness of about 2 mm in the treatment liquid for about 1 to 4 minutes, and then performing vacuum heating at 170 ° C for about 3 hours, it is usually 600 0 from the HNBR surface. m or less.
  • the rubber base material is FKM rubber
  • 100 to 100 parts by weight of acetate is added to 5- to 25 parts by weight of methacrylic modified silicone oil, and dicumyl peroxide is used.
  • a FKM-based rubber substrate with a thickness of about 2 mm is immersed for about 1 to 10 minutes in a treatment solution consisting of 3 parts by weight, and then vacuum-heated at 170 ° C for about 3 hours,
  • the depth (thickness) of the part that is clearly judged to have been modified is usually about 100 nm (nanometer) from the FKM surface. Cinole wood>
  • the sealing material of the present invention can be used for various applications and is not limited to a specific application.
  • it is preferable as a sealing material for a liquid crystal device, a semiconductor manufacturing device, a food industry, and the like. Often used.
  • Sealing materials for furnaces such as diffusion furnaces and lamp annealing devices
  • CVD devices such as metal CVD devices, plasma CVD devices, LP-CVD devices, and sealing materials for sputtering devices
  • transfer equipment for example, wafer transfer equipment (0-ring) or transfer belt
  • plasma-etching equipment plasma-assisting equipment, plasma-enhanced CVD equipment, and equipment requiring plasma resistance, such as wafer transfer equipment, which is an auxiliary equipment of these equipment, are used.
  • wafer transfer equipment which is an auxiliary equipment of these equipment.
  • sealing material for a liquid crystal manufacturing apparatus specifically,
  • Sealing material for snow- and water-ring devices Sealing material for snow- and water-ring devices; Sealing material for CVD equipment (plasma CVD, laser-CVD, etc.); Sealing material for etching equipment (dry etching equipment, penetrating etching equipment, etc.);
  • Sealing material for vapor deposition equipment vacuum vapor deposition equipment, vapor deposition polymerization equipment, etc.
  • Sealing for cleaning equipment dry cleaning type, unit cleaning type
  • Sealing material for exposure equipment (proximity type, stepper type); Sealing material for annealing equipment (lamp annealing equipment, excimer laser annealing equipment, etc.);
  • the sealing material of the present invention can be used for other purposes other than the above, for example,
  • the plasma resistance referred to in the present invention corresponds to a specific type of plasma.
  • the sealing material of the present invention has excellent durability against oxygen plasma and plasma containing oxygen, especially when a silicone-based monomer is used. .
  • a semiconductor can be etched with high accuracy or a resist on a semiconductor can be removed. It can be used for toshing.
  • the sealing material of the plasma processing apparatus is required to have durability against plasma and maintain the vacuum state of the chamber and the like so as not to contaminate products such as wafers.
  • the sealing material of the present invention is also required to have characteristics that make it difficult to release gas and the like from the material itself. In addition to its low friction and non-adhesive properties, it has remarkably excellent plasma resistance to exposure to chemically active plasma.
  • the sealing material for the food industry, it is used for sealing at places where contamination is not expected, such as joint seals for drinking water pipes, and in particular, sticking occurs due to temperature rise etc. It is preferably used in such a use environment.
  • the rubber material Rubber with excellent low friction, non-adhesiveness, abrasion resistance and plasma resistance, while maintaining properties such as rubber elasticity, mechanical strength, elasticity, compression set, deformation followability, and sealability.
  • the surface-modified rubber according to the present invention and the sealing material using the rubber are excellent in low friction, non-adhesion, abrasion resistance, and plasma resistance because they are obtained by the above-mentioned production method.
  • functions derived from the structure of the monomer used such as ozone resistance and oil resistance, can be exhibited.
  • uch sealing materials are used for plasma processing equipment, liquid crystal and semiconductor manufacturing. It can be suitably used as a sealing material for equipment and food industry.
  • the monomers having different compatibility which are difficult to use in the surface polymerization curing method, particularly in Japanese Patent Application Laid-Open No. 4-22039, can be dissolved in the solvent used. If it can be used, it can be easily impregnated and diffused into the rubber substrate (rubber network), and the usable monomer is not particularly limited. Further, in the present invention, it is easy to control the amount of surface modification of the rubber substrate (the modification depth from the surface of the rubber substrate to the inside thereof). For example, since the concentration of the monomer can be adjusted to be thin, it is easy to control the degree of reforming.
  • the rubber substrate is impregnated and diffused irrespective of the compatibility between the rubber substrate and the monomer. Can be done.
  • a fluorine-based or silicon-based monomer which is generally a monomer having poor compatibility with a rubber base material
  • a treatment liquid containing a monomer and a solvent can be used. Therefore, the monomer can be converted to a rubber-based
  • the polymer can be easily impregnated and diffused into the material, and the monomer impregnated in the rubber base material is subjected to thermal decomposition of the polymerization initiator impregnated with the monomer to form the rubber base material. It becomes possible to firmly fix the surface or its vicinity (surface layer) by polymerization reaction.
  • the above-mentioned fluorine-based or silicon-based monomers may be any one kind, or may be two or more kinds of fluorine-based monomers or two or more kinds of silicon-based monomers. It may be either a monomer or a mixture of a fluorine-based monomer and a silicon-based monomer.
  • the polymerization initiator is a radical polymerization catalyst
  • a radical reaction is induced when the radical polymerization catalyst is thermally decomposed, so that the radical reaction proceeds to or near the surface of the rubber substrate (surface layer). It is possible to react and fix more strongly.
  • Examples A1 to A7, B1 to B5, Comparative Examples A1 to A2, B1 to B5 Solutions (treatment liquids) having compositions as shown in Tables 11 to 14 were prepared. After the rubber molded body was immersed in the solution for a predetermined time, a heat treatment was performed in a carbon dioxide gas stream or in a vacuum electric furnace. The composition of the composition is expressed in parts by weight.
  • Rubber base materials used in the processing of 11 to 12 are 70-degree products with a hydrogenated nitrile rubber (HNBR) base, and rubber substrates used in the treatment of Tables 13 to 14 (Examples B1 to B5, In Examples B1 to B5), a 65-degree product containing a fluorine rubber (FKM) base was used.
  • HNBR hydrogenated nitrile rubber
  • Tables 7 to 10 also show the immersion time of the rubber molded product in the solution and the heat treatment conditions.
  • vulcanizate properties such as tensile strength, elongation, and hardness, adhesiveness, friction coefficient, and abrasion loss were measured for the obtained rubber molded body.
  • Adhesive strength was measured under the following measurement conditions using a tacking test machine, lacquer No. 11 manufactured by Less Power Co., Ltd.
  • Measuring conditions Counterpart material: SUS 05, load 0.5 Kgf Z cm 2 (0.049 MPa), separation speed 600 mmZ.min., Temperature 25 ° C or 150 ° C , Pressing time 1 minute and 10 minutes.
  • the friction coefficient of the test object was measured by the method conceptually shown in Fig. 1. That is, a ring-shaped metal SS 41 indicated by reference numeral 3 is set on the upper part of the object to be measured (each vulcanized rubber molded body) 1, and a ring-shaped upper part of the vulcanized rubber molded body 1 from below. With a load of 2 K gf Z cm 2 applied to metal 3, By rotating the metal ring 3 on the vulcanized rubber molded body 1 under the condition of a speed of 0.1 msec, the friction coefficient and the wear amount of the measured object were measured.
  • the wear amount was calculated from the weight change of the sample before and after the friction coefficient measurement described above.
  • Haydon Surface Tester TYPE HEID 0 N-1 4 D (Shinto Using a ball indenter (SUS 06) method, the friction coefficient of the test object (vulcanized rubber molded product) was measured.
  • FIG. 2 shows the principle diagram of this test.
  • a vertical load weight is mounted on a SUS ball via a support member as shown in Fig. 2, and this SUS ball is placed on a rubber sheet with a vertical load weight ( Press with a weight of 200 g). Then, the frictional force generated when the rubber sheet is moved rightward toward the paper is measured.
  • Sample size 100 x 150 x 2 tmm or more rubber sheet (max. 2
  • Test load 200 g (weight for vertical load)
  • Atmosphere 23. C ⁇ 2, 50% ⁇ 10 R H (without condensation in the air conditioning range)
  • Fluoromonomers No, 0- Fluoroalkyl acrylate [2-(N-ethyl chloro-fluoroethyl) ethyl acrylate].
  • Methacryl-modified silicone oil at both ends viscosity 58 cs (25 ° C), specific gravity 0.98, refractive index 1.410, Functional group equivalent 1 6 3 0 g Zm o 1
  • Methacryl-modified silicone oil at both ends viscosity 94 cs (25), specific gravity 0.98, refractive index 1.408,
  • Methacryl-modified silicone oil at one end viscosity 5 cs (25 ° C), specific gravity 0.93, refractive index 1.418, functional group equivalent 420 gmol
  • a solution (treatment liquid) having the composition shown in Table 15 was prepared, and a rubber molded body (fluororubber molded body) was immersed in the solution for a predetermined time, and then heat-treated in a vacuum electric furnace. .
  • the rubber substrates (Examples C1 to C2 and Comparative Examples C1 to C3) used in the treatments in Table 15 are fluoro rubber (FKM) base compounded 65-degree products, and have the following physical properties. Has a value.
  • Comparative Example C2 a rubber base material which had been immersed in acetate before being immersed in the treatment liquid and dried was used.
  • the elastomeric polymer single-chain segment (i) is (ii) vinylidene fluoride / ( ⁇ ) hexafnoreopropylene ⁇ (c) tetrafluoroethylene And its molar ratio (()) / (mouth) Baja)) is 40 to 9075 to 50/0 to 35 (total of 100 moles), and the molecular weight is 30,000 to 1 200,000, and the non-elastomeric polymer chain segment (ii) consists of (chi) ethylene / (li) tetrafluoroethylene Z (nu) hexafluoropropylene
  • the molar ratio ((chi) Beauty) vanu)) is 40 to 60/60 to 40/0 to 30 (total of 100 moles), and the molecular weight is 30,000 to 400,000.
  • the weight ratio of both segments ((i) ba ii)) is 40 to 95/60 to 5 (100 weight parts in total), manufactured by Daikin Industries, Ltd.,
  • Table 15 also shows the immersion time of the rubber molded product in the solution and the heat treatment conditions.
  • the obtained rubber molded body was measured for its vulcanization properties such as tensile strength, elongation, hardness, and chemical resistance, the amount of adhesion, oxygen plasma resistance, and purity (low outgassing properties). Table 15 also shows the measurement results.
  • a gold wire is placed on the mating material (aluminum plate), and a sample (rubber molded body) is placed over a part of the gold wire.
  • the sample was compressed together with the gold wire under the following conditions using a compression jig. Next, the compression was released and the mixture was allowed to cool for 2 hours.
  • Fig. 3 (c) when the gold wire is hooked on the load cell and the aluminum plate of the mating material is moved downward, the maximum value of the force required for the sample to be peeled from the mating material is calculated. It was measured and this was taken as the adhesion.
  • the adhesion was evaluated in five stages, and was evaluated as 1 to 5 in ascending order of the adhesion.
  • Compression time 72 hours
  • Compression temperature 150 ° C
  • the sample was irradiated with oxygen plasma under the following conditions, the weight loss rate of the sample after plasma irradiation was measured, and the plasma resistance was evaluated.
  • the evaluation of plasma resistance was performed in five stages, and was evaluated as 1 to 5 in ascending order of plasma resistance.
  • Purity was evaluated by measuring the amount of gas released from the sample and the mass of the released gas.
  • test sample is placed in a measuring chamber (chamber) at room temperature (25 ⁇ 3 ° C) and under vacuum for 10 hours in the order of 10 — 8 T 0 rr.
  • the change in the internal partial pressure was measured with an ionization vacuum gauge to determine the amount of released gas.
  • the evaluation was performed in five stages, and was evaluated as 1 to 5 in ascending order of the amount of released gas.
  • the evaluation criteria are as follows.
  • the amount of gas released from the chamber is subtracted from the amount of gas released from the chamber, and the amount of gas released from the sample is taken as the mass spectrum of the amount of gas released from the sample. It was measured with an analyzer. These measurement conditions are shown below.
  • Weight reduction rate 5 grades 1 1 5 5 5
  • the method for producing a surface-modified rubber according to the present invention employs a compression set, rubber elasticity, mechanical strength, It is useful for obtaining rubber excellent in low friction, non-adhesiveness, abrasion resistance and plasma resistance while maintaining deformation followability, and the surface-modified rubber obtained by the production method of the present invention is, for example, It can be widely used as a sealing material for semiconductor manufacturing equipment, chemical liquid piping and tanks, food manufacturing equipment, etc.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Sealing Material Composition (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention porte sur un caoutchouc modifié en surface, capable de former un caoutchouc moulé qui conserve les propriétés inhérentes au caoutchouc proprement dit telles que la résistance, la rémanence par la compression, des propriétés d'étanchéité et des propriétés associées à sa déformation. Ce caoutchouc modifié n'est, en outre, pas poisseux, présente des caractéristiques de faible friction et une excellente résistance à l'usure et au plasma. Le procédé de production de ce caoutchouc consiste à mettre en contact une base de caoutchouc avec un traitement comprenant un monomère possédant une double liaison polymérisable, un initiateur de polymérisation et un solvant, à chauffer la base de caoutchouc obtenue pour polymériser le monomère et modifier ainsi la surface et les parties avoisinant la base de caoutchouc.
PCT/JP1997/004831 1997-01-10 1997-12-25 Procede de production de caoutchouc modifie en surface, caoutchouc modifie en surface et materiau d'etancheite WO1998030622A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP97950398A EP0890601B1 (fr) 1997-01-10 1997-12-25 Materiau d'etancheite a base de caoutchouc fluore modifie en surface
US09/142,531 US6074698A (en) 1997-01-10 1997-12-25 Process for producing surface-modified rubber, surface-modified rubber, and sealing material
KR1019980707108A KR100525065B1 (ko) 1997-01-10 1997-12-25 표면개질고무의제조방법,표면개질고무및실링재
DE69735938T DE69735938T2 (de) 1997-01-10 1997-12-25 Oberflächenmodifiziertes fluorokautschukdichtungsmaterial
HK99104303A HK1019153A1 (en) 1997-01-10 1999-10-04 Process for producing surface-modified rubber, surface-modified rubber, and sealing material.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP312197 1997-01-10
JP9/3121 1997-01-10
JP9/276257 1997-10-08
JP27625797 1997-10-08

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WO1998030622A1 true WO1998030622A1 (fr) 1998-07-16

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EP0890601B1 (fr) 2006-05-24
HK1019153A1 (en) 2000-01-14
DE69735938D1 (de) 2006-06-29
EP0890601A1 (fr) 1999-01-13
EP0890601A4 (fr) 2000-12-20
KR100525065B1 (ko) 2006-04-14
CN1213389A (zh) 1999-04-07
US6074698A (en) 2000-06-13
TW502051B (en) 2002-09-11
DE69735938T2 (de) 2007-01-25
CN1154684C (zh) 2004-06-23
KR20000044031A (ko) 2000-07-15

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